EP0107275B1 - Preparation of mn3o4 - Google Patents
Preparation of mn3o4 Download PDFInfo
- Publication number
- EP0107275B1 EP0107275B1 EP83304355A EP83304355A EP0107275B1 EP 0107275 B1 EP0107275 B1 EP 0107275B1 EP 83304355 A EP83304355 A EP 83304355A EP 83304355 A EP83304355 A EP 83304355A EP 0107275 B1 EP0107275 B1 EP 0107275B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- manganese
- preparing
- reduction
- set forth
- manganese oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000002360 preparation method Methods 0.000 title description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 229910003174 MnOOH Inorganic materials 0.000 claims description 7
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 abstract description 16
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- -1 manganite Chemical compound 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
Definitions
- the invention relates to an improved process for preparing Mn 3 0 4 by the controlled reduction of higher manganese oxides.
- Mn 3 0 4 has been produced by sintering manganese (II) oxide in the presence of oxygen.
- Manganese (II) oxide may be produced by heating manganese (11) carbonate, or by heating manganese dioxide.
- the present invention provides an improved process for the preparation of Mn 3 0 4 , by the reduction of higher manganese oxides. Unlike prior processes, which were generally conducted at red heat, the present process is characterized by a relatively low temperature in the range from about 250° to about 550°C, depending on the starting material.
- the starting material is a higher manganese oxide, such as manganite, MnOOH. It has been found that the reduction of a higher manganese oxide may be controlled to recover Mn 3 0a.
- the Mn 3 0 4 produced by the present invention is useful as a source of manganese for the production of ferrites.
- the two-step reduction of a higher manganese oxide may be stopped after the first step, to recover Mn 3 0 4 .
- Mn 3 0 4 by the reduction of higher manganese oxides is surprising, since thermodynamic calculations suggest that it is not possible to effect a step-wise reduction of higher manganese oxides, such as Mn0 2 , Mn 2 0 3 , MnOOH, or other intermediate manganese oxides having an oxygen ratio above MnO 1.33 to Mn 3 O 4 .
- Mn 3 O 4 has a manganese to oxygen ratio of MnO 1.33 .
- methane as a reducing gas permits a practical step-wise reduction of higher manganese oxides to Mn 3 0 4 .
- Other reducing gases such as carbon monoxide or hydrogen do not allow the two-step reduction process when performed on a commercially acceptable scale to be stopped after the first step, to recover Mn 3 0 4 .
- GB-A-1202971 discloses using a mixture of air and methane in a ratio of 2:1 to 4:1 to produce MnO from higher oxides.
- higher manganese oxides refers to manganese oxides having an oxygen ratio above MnO 1.33 .
- the higher manganese oxide to be reduced is heated, in a kiln, in the presence of an excess current of methane gas.
- the temperature to which the higher manganese oxide should be heated ranges from about 250°C to about 550°C, depending upon the specific higher manganese oxide to be reduced.
- manganese dioxide, Mn0 2 should be heated to a temperature from about 250°C to about 400°C.
- temperatures from about 300°C to 500°C should be used. In general, higher temperatures produce larger product particles and/or increased crystallinity.
- the reduction of a higher manganese oxide in the presence of an excess of methane gas is conducted at temperatures below about 500°C to facilitate stopping the two-step reduction after the first step, to recover Mn 3 0 4 .
- prior processes required the reoxidation of manganese (II) to produce Mn 3 0 4 .
- These prior processes required much higher temperatures, up to about 700°C, and therefore resulted in a loss of surface area and activity of the Mn 3 0 4 product because of sintering.
- the process of the present invention is a significant improvement over the prior process because it permits the reduction of higher oxides of manganese to Mn 3 0 4 at relatively low temperatures, well below sintering temperatures.
- the reduction of manganite, MnOOH to Mn 3 0 4 was conducted in the presence of a flowing current of excess methane gas, at temperatures ranging from 310°C to 550°C.
- the manganese to oxygen ratio of the product produced in each case is set forth below, and illustrated in the accompanying graph.
Abstract
A process of preparing Mn3O4, by the reduction of higher manganese oxides, using methane as a reducing gas under controlled temperatures.
Description
- The invention relates to an improved process for preparing Mn304 by the controlled reduction of higher manganese oxides.
- Mn304 has been produced by sintering manganese (II) oxide in the presence of oxygen. Manganese (II) oxide may be produced by heating manganese (11) carbonate, or by heating manganese dioxide.
- These prior methods for the preparation of Mn304 require high temperatures to sinter the manganese (II) oxide. In addition, it is obviously inefficient to reduce manganese dioxide to manganese (II) oxide, and then re-oxidize manganese (II) oxide to produce Mn304.
- The present invention provides an improved process for the preparation of Mn304, by the reduction of higher manganese oxides. Unlike prior processes, which were generally conducted at red heat, the present process is characterized by a relatively low temperature in the range from about 250° to about 550°C, depending on the starting material. The starting material is a higher manganese oxide, such as manganite, MnOOH. It has been found that the reduction of a higher manganese oxide may be controlled to recover Mn30a.
- The reduction of a higher manganese oxide, such as manganite, occurs in two steps: a relatively fast step producing Mn304, followed by a slower second step producing manganese (II) oxide.
- The Mn304 produced by the present invention is useful as a source of manganese for the production of ferrites.
- It is a feature of the present invention that the two-step reduction of a higher manganese oxide may be stopped after the first step, to recover Mn304.
- It is an advantage of the present invention that it permits a relatively low temperature reduction of a higher manganese oxide.
- It is another advantage of the present invention that it is a dry process, much simpler to carry out than alternate wet processes involving the precipitation of manganese (II) hydroxide.
- Still other advantages of the invention will be readily apparent to those of ordinary skill in the art from the detailed description of the invention which follows.
- The process for the preparation Mn304 by the reduction of higher manganese oxides is surprising, since thermodynamic calculations suggest that it is not possible to effect a step-wise reduction of higher manganese oxides, such as Mn02, Mn203, MnOOH, or other intermediate manganese oxides having an oxygen ratio above MnO1.33 to Mn3O4. Mn3O4 has a manganese to oxygen ratio of MnO1.33. Surprisingly, it has been found that using methane as a reducing gas permits a practical step-wise reduction of higher manganese oxides to Mn304. Other reducing gases such as carbon monoxide or hydrogen do not allow the two-step reduction process when performed on a commercially acceptable scale to be stopped after the first step, to recover Mn304.
- Nouveau Traite de Chimie Mineral 16 p. 794 1960-described a method of preparing Mn304 by the reduction of Mn02 using H2 at 230°C on a laboratory scale. However such a method is not commercially acceptable since it cannot be performed on an industrial scale.
- GB-A-1202971 discloses using a mixture of air and methane in a ratio of 2:1 to 4:1 to produce MnO from higher oxides.
- The process for the preparation of Mn304 by the reduction of Mn203 or Mn02 may be described by the equations:
- Similar equations apply to the reduction of MnOOH and other higher manganese oxides in the presence of methane gas to produce Mn304. As used herein the term higher manganese oxides refers to manganese oxides having an oxygen ratio above MnO1.33.
- In accordance with the present invention, the higher manganese oxide to be reduced is heated, in a kiln, in the presence of an excess current of methane gas. The temperature to which the higher manganese oxide should be heated ranges from about 250°C to about 550°C, depending upon the specific higher manganese oxide to be reduced. For example, it has been found that manganese dioxide, Mn02, should be heated to a temperature from about 250°C to about 400°C. In case Mn203 or MnOOH is to be reduced to Mn304, it is found that temperatures from about 300°C to 500°C should be used. In general, higher temperatures produce larger product particles and/or increased crystallinity. However, it has been found that at temperatures above about 550°C, it is not practical to stop the two-step reduction, to recover Mn304. Preferably the reduction of a higher manganese oxide in the presence of an excess of methane gas is conducted at temperatures below about 500°C to facilitate stopping the two-step reduction after the first step, to recover Mn304.
- As described above, prior processes required the reoxidation of manganese (II) to produce Mn304. These prior processes required much higher temperatures, up to about 700°C, and therefore resulted in a loss of surface area and activity of the Mn304 product because of sintering. The process of the present invention is a significant improvement over the prior process because it permits the reduction of higher oxides of manganese to Mn304 at relatively low temperatures, well below sintering temperatures.
- The reduction of manganite, MnOOH to Mn304 was conducted in the presence of a flowing current of excess methane gas, at temperatures ranging from 310°C to 550°C. The manganese to oxygen ratio of the product produced in each case is set forth below, and illustrated in the accompanying graph.
Claims (9)
1. A process of preparing Mn304 by reduction of a higher manganese oxide using a gaseous reducing agent characterised in that the process comprises the steps of:
immersing a higher manganese oxide in a flow of a reducing gas containing methane,
heating said higher manganese oxide in said flow reducing gas containing methane to temperature from 250°C to 550°C, and recovering Mn304.
2. The process of preparing Mn304 set forth in claim 1, wherein said reducing gas consists essentially of methane.
3. The process of preparing Mn304 set forth in claim 1 or 2, wherein said higher manganese oxide is heated to a temperature from 250°C to 500°C.
4. The process of preparing Mn304 set forth in claim 1 or 2, wherein said higher manganese oxide is . Mn02.
5. The process of preparing Mn304 set forth in claim 4 wherein said Mn02 is heated to a temperature from 250°C to 400°C.
6. The process of preparing Mn304 set forth in claim 1 or 2, wherein said higher manganese oxide is Mn203.
7. The process of preparing Mn304 set forth in claim 6, wherein said Mn203 is heated to a temperature from 300°C to 500°C.
8. The process of preparing Mn304 set forth in claim 1 or 2, wherein said higher manganese oxide is MnOOH.
9. The process of preparing Mn304 set forth in claim 8, wherein said MnOOH is heated to a temperature from 300°C to 500°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83304355T ATE26434T1 (en) | 1982-09-30 | 1983-07-27 | PRODUCTION OF TRIMANGANTETROXIDE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US430525 | 1982-09-30 | ||
| US06/430,525 US4411878A (en) | 1982-09-30 | 1982-09-30 | Preparation of Mn3 O4 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0107275A1 EP0107275A1 (en) | 1984-05-02 |
| EP0107275B1 true EP0107275B1 (en) | 1987-04-08 |
Family
ID=23707906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83304355A Expired EP0107275B1 (en) | 1982-09-30 | 1983-07-27 | Preparation of mn3o4 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4411878A (en) |
| EP (1) | EP0107275B1 (en) |
| JP (1) | JPS5964529A (en) |
| AT (1) | ATE26434T1 (en) |
| DE (1) | DE3370790D1 (en) |
| ZA (1) | ZA835195B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2596042A1 (en) * | 1986-03-19 | 1987-09-25 | Ballouhey Marcel | Process for the preparation of gamma manganese sesquioxide |
| US4812302A (en) * | 1987-06-15 | 1989-03-14 | Kerr-Mcgee Chemical Corporation | Process for preparing high purity Mn3 O4 |
| US6610263B2 (en) | 2000-08-01 | 2003-08-26 | Enviroscrub Technologies Corporation | System and process for removal of pollutants from a gas stream |
| IL143551A0 (en) * | 2001-06-04 | 2002-04-21 | Pigmentan Ltd | Paints and coatings composition useful for corrosion inhibition and a method for production therefor |
| US7232782B2 (en) | 2002-03-06 | 2007-06-19 | Enviroscrub Technologies Corp. | Regeneration, pretreatment and precipitation of oxides of manganese |
| US20030059460A1 (en) * | 2001-09-27 | 2003-03-27 | Yasuhiko Tabata | Hybrid material for regeneration of living body tissue |
| WO2003072241A1 (en) | 2001-12-21 | 2003-09-04 | Enviroscrub Technologies Corporation | Pretreatment and regeneration of oxides of manganese |
| BRPI0407007A (en) | 2003-01-28 | 2006-01-10 | Enviroscrub Technologies Corp | Method and system for fast and adaptable processing of manganese oxides and integrated sorbent processing and pollution control system |
| US7488464B2 (en) | 2003-07-31 | 2009-02-10 | Enviroscrub Technologies Corporation | Metal oxide processing methods and systems |
| CN101219809B (en) * | 2007-12-12 | 2010-06-09 | 中国科学院长春应用化学研究所 | Process for producing mangano-manganic oxide nanocrystalline with controllable sizing and shape |
| CN102259928B (en) * | 2011-05-20 | 2013-02-20 | 浙江大学 | Method for preparing Mn3O4 nano-particles |
| CN102502849A (en) * | 2011-10-31 | 2012-06-20 | 上海理工大学 | Method for preparing Mn3O4 and composite nano material thereof by using manganous salt as raw material |
| CN115140774A (en) * | 2022-08-09 | 2022-10-04 | 贵州金瑞新材料有限责任公司 | Preparation method of mangano-manganic oxide |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1937488A (en) * | 1932-10-01 | 1933-11-28 | Intermetal Corp | Manganese dioxide |
| US2103219A (en) * | 1935-01-30 | 1937-12-21 | Leslie G Jenness | Controlled catalytic oxidation |
| US2103221A (en) * | 1935-11-14 | 1937-12-21 | Intermetal Corp | Oxidation catalysts and process |
| CH278931A (en) * | 1944-12-26 | 1951-11-15 | Fondal Jacques | Process for the reduction of higher oxides of manganese. |
| US3361531A (en) * | 1967-02-27 | 1968-01-02 | Union Carbide Corp | Removal of oxygen from gas mixtures |
| GB1202971A (en) * | 1968-01-26 | 1970-08-26 | Picklands Mather & Co | REDUCING TO MnO THE MnO<2> OF A MANGANESE ORE |
| GB1374975A (en) * | 1970-11-30 | 1974-11-20 | Kodak Ltd | Preparation of trimanganese tetroxide |
| US3715764A (en) * | 1971-05-13 | 1973-02-13 | Bethlehem Steel Corp | High porosity manganese oxide pellets |
| US3767780A (en) * | 1972-02-03 | 1973-10-23 | Eastman Kodak Co | Preparation of manganese oxides |
| US3950505A (en) * | 1975-04-28 | 1976-04-13 | Diamond Shamrock Corporation | Preparation of manganous hydroxide |
| US4010236A (en) * | 1975-07-21 | 1977-03-01 | Diamond Shamrock Corporation | Manganese ore reduction |
-
1982
- 1982-09-30 US US06/430,525 patent/US4411878A/en not_active Expired - Fee Related
-
1983
- 1983-07-18 ZA ZA835195A patent/ZA835195B/en unknown
- 1983-07-19 JP JP58133029A patent/JPS5964529A/en active Pending
- 1983-07-27 DE DE8383304355T patent/DE3370790D1/en not_active Expired
- 1983-07-27 EP EP83304355A patent/EP0107275B1/en not_active Expired
- 1983-07-27 AT AT83304355T patent/ATE26434T1/en not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| NOUVEAU TRAITE DE CHIMIE MINERALE - VOLUME 16, Page 794, MASSON- PARIS (1960) - PASCAL(EDITOR) * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5964529A (en) | 1984-04-12 |
| DE3370790D1 (en) | 1987-05-14 |
| US4411878A (en) | 1983-10-25 |
| EP0107275A1 (en) | 1984-05-02 |
| ZA835195B (en) | 1984-04-25 |
| ATE26434T1 (en) | 1987-04-15 |
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